Additive and vehicle for inks, paints, coatings and adhesives

ABSTRACT

An environmentally safe additive and vehicle system are provided for water-based and oil-based printing inks, paints, coatings and adhesives which can be rapidly transferred, dispersed, dispensed, spread, dried and cured. The low cost, stable additive and vehicle system enhance multiple color, high speed printing with sharp, highly defined images and superior quality, and can be used on many different types of substrates, such as paper, paperboard, cardboard, clay coated board, foil, plastic, glass, metal, wood and composites. The additive may be formed by the reaction product of a photoinitiator, such as an UV-activated polyelectrolyte, and a monomer, such as an acrylate or a methacrylate in an aqueous solution. In other embodiments, the additive is formed from a carboxylic acid or anhydride and alkylalkanolamine monomer or a dialkylaminoalkyl acrylate or methacrylate monomer in an aqueous solution.

The present patent document is a division of application Ser. No.11/009,577, filed Dec. 10, 2004, now U.S. Pat. No. 7,863,485 which ishereby incorporated by reference.

TECHNICAL FIELD

The technical field of the invention is that of additives and vehiclesfor inks. The additives and vehicles may be used in waterborne inks formany types of printing, including flexographic, gravure, offsetlithographic, and letterpress printing. The additives and vehicles mayalso be used in coatings, paints, and adhesives.

BACKGROUND

This invention pertains to aqueous polymeric compositions and, moreparticularly, to an additive and vehicle system for water based printinginks, paints, coatings and adhesives.

It is important to minimize, if not eliminate, volatile organic compound(VOCs) from paints, printing inks, coatings, and adhesives. Fumesemitted from such materials can be hazardous to the health andwell-being of workers in paint manufacturing plants, printing companies,coating shops, and adhesive facilities. These fumes can be caused byflashing and vaporizing of solvents and free monomers. Furthermore,prolonged exposure to volatile emissions can impair the sight or brainfunction, and internal organs of people exposed to the volatileemissions. Some VOCs are also carcinogenic. It is often recommended thatconsumers using paints, printing inks, coatings, adhesives, and likematerials, do so outside or in a well ventilated area to decrease healthrisks and injury. This is not always possible, particularly inwintertime or if the work is going to be done outside.

Not only can VOCs be injurious to the health and welfare of society, butspecific amounts of VOCs are often prohibited or controlled byenvironmental laws. Moreover, products containing VOCs often cause wastedisposal problems and expensive cleanup costs to comply with localanti-dumping ordinances and environmental regulations.

It is also desirable that printing inks, coatings, paints, and adhesivescan be rapidly transferred, dispersed, dispensed, spread, and dried toincrease throughput and production. This is especially important forfour color printing on Gravure presses. Multiple color printing shouldhave enough tack with yellow pigments to trap and avoid splattering ofred pigments and subsequent dispersants. Furthermore, it is desirablethat vehicles or carriers for printing inks, to coatings, paints andadhesives be rewettable or resolubilize so they do not stick to, gum upor clog printing presses and production equipment causing undesireddowntime, decreased output, repairs and expense. Many conventionalprinting inks, paints, coatings, and adhesives become unstable duringstorage, which can lead to phase separation, layering, loss of quality,and delamination of the product.

Latex-based ink technology developed by Robert Slocombe is disclosed inU.S. Pat. Nos. 4,374,670 and 4,414,354. The Slocombe technology providedan approach which promised to solve some basic problems associated withwaterborne inks and coatings. Among the promised benefits of theSlocombe technology were adhesion to low energy surfaces, high speedprinting, and the ability to disperse most pigments.

The promise of the Slocombe technology was never realized for a numberof reasons. The Slocombe technology centers around the high degree offree monomers which are present in Slocombe's product. The Slocombetechnology is also limited to rubber-based resins. Slocombe's technologyfurther needed to be activated by ultraviolet radiation which was notpreviously available. Slocombe's three component system had a limitedpot life once the components were mixed together. Slocombe's inksfurther require a cosolvent to incorporate an initiator, polyelectrolyteand latex into a miscible solution. Moreover, Slocombe's cosolvents wereunstable volatile organic solvents which are undesirable from anenvironmental viewpoint. Slocombe's polyelectrolyte interaction was alsoinefficient, and often amounted to 15%-25% of the resin formulation.These expensive compounds often resulted in inks which were too costlyto be economically viable.

It is therefore desirable to provide an improved vehicle system for usein water-based printing inks, paints, coatings and adhesives, whichavoids substantial use of solvents and volatile organic compounds, andovercomes most, if not all, of the preceding problems.

BRIEF SUMMARY

One embodiment is an additive that includes an aqueous solution of thereaction product of: (i) a first reagent including at least one materialselected from the group consisting of a carboxylic acid and ananhydride, and (ii) a second reagent including at least one materialselected from the group consisting of an alkyl alkanolamine monomer, adialkylaminoalkyl acrylate monomer, and a dialkylaminoalkyl methacrylatemonomer.

Another embodiment is an additive that includes an aqueous solution ofthe reaction product of (i) a first reagent including at least onematerial selected from the group consisting of a carboxylic acidcontaining a benzene ring and an anhydride containing a benzene ring,and (ii) a second reagent including at least one material selected fromthe group consisting of a dialkylaminoalkyl acrylate monomer and adialkylaminoalkyl methacrylate monomer.

Another embodiment is a method of forming an additive, the methodincluding forming an aqueous solution of a first reagent or a secondreagent, and adding the other of the first reagent and the secondreagent to the aqueous solution, wherein the first reagent includes atleast one material selected from the group consisting of a carboxylicacid and an anhydride, and the second reagent includes at least onematerial selected from the group consisting of an alkylalkanolaminemonomer, a dialkylaminoalkyl acrylate monomer, and a dialkylaminoalkylmethacrylate monomer, and wherein the first reagent and the secondreagent react to form the additive.

Another embodiment includes a vehicle system that includes by weight:(a) about 4-45% of a first component, the first component including atleast one material selected from the group consisting of an acrylicresin solution, a latex solution, a urethane solution, amicrocrystalline wax solution, and a vegetable oil; (b) about 50-90% ofa second component, the second component including at least one materialselected from the group consisting of a fumaric resin solution and anacrylic resin emulsion; and (c) about 0.5-10% of an aqueous solution ofan additive comprising the reaction product of (i) a first reagentcomprising at least one material selected from the group consisting of acarboxylic acid and an anhydride; and (ii) a second reagent including atleast one material selected from the group consisting of an alkylalkanolamine monomer, a dialkylaminoalkyl acrylate monomer, and adialkylaminoalkyl methacrylate monomer.

Another embodiment includes a vehicle system that includes by weight:(a) about 4-45% of a first component including at least one materialselected from the group consisting of an acrylic resin solution, a latexresin solution, a paraffin solution, a paraffin emulsion, a urethaneresin solution, and a vegetable oil; (b) about 50-90% of a secondcomponent including at least one material selected from the groupconsisting of a fumaric resin solution and an acrylic resin emulsion;and (c) about 0.5-10% additive in aqueous solution including thereaction product of (i) a first reagent including at least one materialselected from the group consisting of a carboxylic acid containing abenzene ring and an anhydride containing a benzene ring; and (ii) asecond reagent including at least one material selected from the groupconsisting of an alkylaminoalkyl acrylate monomer and an alkylaminoalkylmethacrylate monomer.

Another embodiment is a vehicle system including by weight: (a) about80-99% of a first component including at least one material selectedfrom the group consisting of an acrylic resin solution, a urethane resinsolution, a latex resin solution, a latex resin emulsion, a waxdispersion or emulsion, a fumaric resin solution, and a vegetable oil;and (b) about 1-20% additive including in aqueous solution the reactionproduct of (i) a first reagent including at least one material selectedfrom the group consisting of a carboxylic acid and an anhydride; and(ii) a second component including at least one material selected fromthe group consisting of a dialkylaminoalkyl acrylate monomer, adialkylaminoalkyl methacrylate monomer, and an alkyl alkanolaminemonomer.

An improved additive and vehicle system are provided which areparticularly useful for water-based and aqueous polymer printing inks,paints, coatings and adhesives (bonding agents). The vehicle systemcontaining the additive can also be used as a laminating adhesive, heatseal adhesive, bonding agent, or glue, such as a white glue.Advantageously, the improved additive and vehicle system substantiallyavoids the use or need of harmful solvents, free monomers, and volatileorganic compounds (VOCs), such as isopropyl alcohol. The inventiveadditive and vehicle system can be used on numerous substrates, such aspaper, paperboard, cardboard, clay coated board, foil, plastic, glass,metal, wood, and composites. Desirably, the additive and vehicle systemare environmentally safe, economical, attractive, and effective.

Significantly, the inventive additive and vehicle system acceleratescuring to allow for faster high quality printing. The additive andvehicle system also facilitate flocculation and VOC-free ink. When inkscomprising a vehicle system containing the additive are transferred to asubstrate such as paper, phase separation occurs and the polymer solidcompounds adhere to the substrate. Liquid (e.g., water) is liberated,vaporized, and removed by air circulation and/or heat, and the coalescedpolymer is cured. The vehicle system and additive are very stable, havea long shelf life, and can be made without a precursor. The vehiclesystem is particularly useful for waterborne or water-based systems andmedia with a pH between 7 and 14 and with less than 1% isopropanol.

To this end, the special vehicle system includes: (1) an acrylic resinsolution; (2) a fumaric resin solution or an acrylic resin emulsion; and(3) an additive formed from a monomer and a carboxylic acid oranhydride, such as a photoinitiator. The vehicle system can alsoinclude: one or more of (4) a defoamer, (5) a surfactant, and (6) aninhibitor.

The acrylic resin solution can comprise an acrylic solution resin,water, and a diluent. The fumaric resin solution can comprise a fumaricresin, water, and a diluent. The acrylic resin emulsion can comprise anacrylic emulsion resin and water. The diluent can be a cutting agentsuch as ammonia, monoethanolamine (MEA), dimethylethanolamine (DMEA),triethanolamine (TEA), morpholine, propylene glycol and polypropyleneglycol.

The monomer can be an acrylate or methacrylate, such as adialkylaminoalkyl acrylate or methacrylate, for example,dimethylaminoethyl, diethylaminoethyl, or diethylaminopropyl acrylate ormethacrylate. Alternatively, the monomer may be an alkyl alkanolaminemonomer.

The carboxylic acid or anhydride, or photoinitiator, can be anultraviolet responsive photoinitiator, such as4,4′-carbonylbis(1,2-benzene-dicarboxylic acid);3,3′,4,4′-tetracarboxy-benzophenone;3,3′,4,4′-benzophenonetetracarboxylic acid;benzophenonetetracarboxyldiphthalic acid; 4,4′-carboxydipthalic acid;benzophenonetetracarboxylic dianhydride; or orthobenzoylbenzoic acid.The photoinitiator may include a carboxylic acid or anhydride containingcompound such as acrylic acid, benzoic acid, catechuic acid(3,4-dihydroxy benzoic acid), hydroxybenzoic acid, formic, acid, acetic,acid, propionic acid, oxalic acid, chloracetic acid, phthalic anhydride,salicylic acid, acetylsalicylic acid, 2,4-dichlorophenoxyacetic acid,acrylic acid, gluconic acid, adipic acid, maleic anhydride, fumaricacid, malonic acid, stearic acid, oleic acid, methacrylic acid, itaconicacid, sebacic acid, succinic acid, citric acid, tartaric acid, abieticacid, napthenic acid, palmitic acid, hydroxy acid, glycolic acid, lacticacid, ricinoleic acid (castor oil acid), maleic acid, protocatechoicacid, gallic acid, cinnamic acid, hydroxycinnamic, caffeic acid, or bileacid. Obviously, any processing that involves a photoinitiator must beaccomplished in the absence of light, and the finished compounds arepreferably kept out of the light and stored in dark or opaquecontainers.

In one preferred form, the monomer comprises dimethylaminoethylmethacrylate, the acrylic resin solution comprises a styrene acryliccopolymer, and the acrylic resin emulsion comprises a styrene acryliccopolymer emulsion.

In another embodiment, an additive useful in formulating inks, paints,coatings and adhesives includes an aqueous solution of carboxylic acidor anhydride compound, to which is added an alkylalkanolamine monomer,or a dialkyl alkanolamine acrylate or methacrylate monomer or dimer.Another embodiment includes a method of preparing the additive byforming an aqueous solution or slurry of the carboxylic acid oranhydride and slowly adding the amine or acrylate monomer or dimer. Theamine or acrylate is added slowly to control the exotherm.

In another embodiment, an additive useful in formulating inks, paints,coatings and adhesives includes an aqueous solution of a benzenering-containing carboxylic acid or anhydride compound, to which is addeda dialkylaminoalkyl acrylate or methacrylate monomer or dimer. Anotherembodiment includes a method of preparing the additive by forming anaqueous solution or slurry of the benzene-ring containing carboxylicacid or anhydride and slowly adding the amine or acrylate monomer ordimer.

In another embodiment, an additive useful in formulating inks, paints,coatings and adhesives includes an aqueous solution of a carboxylic acidor anhydride compound, to which is added a alkyl alkanolamine acrylateor methacrylate monomer. Another embodiment includes a method ofpreparing the additive by forming an aqueous solution or slurry of thecarboxylic acid or anhydride and slowly adding the acrylate monomer.

In another embodiment, an additive useful in formulating inks, paints,coatings and adhesives includes an aqueous solution of carboxylic acidor anhydride compound, to which is added an alkylalkanolamine monomer,or a dialkyoaminoalkyl acrylate or methacrylate monomer or dimer.Another embodiment includes a method of preparing the additive byforming an aqueous solution or slurry of the carboxylic acid oranhydride and slowly adding the amine or acrylate monomer or dimer.

The inventive vehicle system has produced unexpected surprisingly goodresults. A more detailed explanation of the invention is provided in thefollowing description and claims.

DETAILED DESCRIPTION OF THE PRESENTLY PREFERRED EMBODIMENTS

A vehicle system substantially free of volatile compounds (VOCs) isformed for use in the manufacture of inks, coatings, paints, and bycombining an additive with a first solution and a second solution oremulsion. The first resin solution may be an acrylic resin solution, alatex resin solution, or a vegetable oil resin solution. The secondresin may be a fumaric resin solution or may be an acrylic resinemulsion.

A vehicle system additive comprising a non-VOC additive is added to thevehicle system to cause the other polymers to coalesce or to flocculate.The additive also assists in the rewetting of the vehicle.

A surfactant can be added to the vehicle system in order to reduce theliquid surface tension to almost that of solvent products or about 20dynes/cm.

An inhibitor can be added to the vehicle system to prevent liquid inkfrom sticking in the cells of Gravure cylinders in the printing press.The inhibitor serves as a lubricant and also assists in the preventionof rust or oxidation of metal parts, in the printing press or otherapplicator. The inhibitor may also act to control coalescence of the inkor coating, i.e. to delay flocculation or phase separation, when slowerdrying or oxidation is desired.

As soon as the liquid of the vehicle system is applied to the substrate,in the presence of air, heat, or light, flocculation (phase separation)occurs and films arc formed. The vehicle system is believed to providetwo films. The first film causes the polymer to coalesce. The secondfilm is protective and prevents fading of the ink, paint, etc. Theliquid is liberated, vaporized or otherwise removed by air and/or heat.Unlike solvent based systems, the product (vehicle system) usually curesinstead of dries.

The improved inventive vehicle system for aqueous polymer printing inks,paints, coatings and adhesives, includes by weight: 1-10% additive;4-45% first acrylic resin solution; and 50-90% fumaric resin solution,or 50-90% acrylic resin emulsion. In a preferred form, the improvedvehicle system comprises by weight: 2-6% additive; 15-35% acrylic resinsolution; and 60-80% fumaric resin solution or 60-80% acrylic resinemulsion. Most preferably, for best results, the vehicle systemcomprises by weight: 2.5%-5% additive; 20-30% acrylic resin solution,and 65%-75% fumaric resin solution or 65-75% acrylic resin emulsion.

Instead of using the acrylic resin solution, excellent results are alsoobtained for a water-based ink when the vehicle system includes 4-45%latex or waterborne solution, 50-90% fumaric resin solution, and 2-5%additive. Examples of suitable waterborne resins include urethanes andparaffins. In another alternative, excellent results are obtained whenthe vehicle system includes 4-45% vegetable oil, 50-90% fumaric resinsolution or acrylic resin emulsion, and 2-5% additive. Suitablevegetable oils include at least soybean oil and linseed oil. If awater-based paint is desired, good results may be obtained by using5-10% of the additive, rather than a smaller amount, in formulationsusing acrylic resin, vegetable oil, latex, and urethanes as the firstcomponent. Coatings and adhesives may be formulated by substitutingappropriate resins, primarily as the first component in the vehiclesystem. Emulsions of microcrystalline may also be used.

For paper substrates, fumaric resin compounds are preferably used in thevehicle system. For films and foil substrates, acrylic emulsion resinsare preferably used in the vehicle system.

The vehicle system may also comprise by weight: a defoamer in an amountup to 1%, a surfactant in an amount up to 1%, an inhibitor in an amountup to 2%, and the vehicle system preferably comprises 0.05-0.15%defoamers, 0.05-0.15% surfactants, and 0.1-0.3% inhibitors. Sincewater-based printing inks have a tendency to foam, a defoamer ispreferably added to the vehicle system on or before the vehicle systemis put on a printing press, such as a Gravure printing press. Asurfactant can be added to the vehicle system to decrease surfacetension of the vehicle, increase transfer speed of the vehicle systemfrom the applicator (e.g. printing press) to the substrate, enhancedispersion of the liquid and color dispersants (pigments), and improvespreading (trapping).

Advantageously, the vehicle system can be blended with almost anywater-based color dispersion, ink or colorant that contains less than 1%isopropyl alcohol (isopropanol), and can run at over 2000 feet/min on aGravure printing press.

Additive

An additive for a vehicle system solves the problem discussed above byreplacing free monomers with an additive. This additive is unique inthat it is water soluble and also allows it to be compatible with a widevariety of polymeric vehicle systems. The additive has also been founduseful when mixed directly into already-formulated inks and coatings.

The vehicle system additive comprises a monomer and a carboxylic acid oranhydride compound. The monomer can be an acrylate or a methacrylate,such as dialkylaminoalkyl acrylate or methacrylate, for example,dimethylaminoethyl acrylate or methacrylate, diethylaminoethyl acrylateor methacrylate, or diethylaminopropyl acrylate or methacrylate.Alternatively, the monomer may be an alkylalkanolamine, such asN,N-dimethylethanolamine.

a. Aromatic and Non-Aromatic Carboxylic Acid or Anhydride-ContainingCompounds.

The carboxylic acid or anhydride-containing compound is preferably aphotoinitiator, such as an ultraviolet (UV) responsive photoinitiator,such as 4,4′-carbonylbis (1,2-benzenedicarboxylic acid);3,3′,4,4′-tetracarboxybenzophenone; 3,3′4,4′-benzophenonetetracarboxylicacid; benzophenonetetracarboxyldipthalic acid: 4,4′-carboxydipthalicacid; benzophenonetetracarboxylic dianhydride; and orthobenzoylbenzoicacid. The acid or anhydride may instead be a simpler carboxylic acid oranhydride containing compound such as benzoic acid, hydroxybenzoic acid,catechuic acid (3,4-dihydroxybenzoic acid), formic acid, acetic acid,propionic acid, oxalic acid, chloracetic acid, phthalic anhydride,salicylic acid, acetylsalicylic acid, 2,4-dichlorophenoxyacetic acid,acrylic acid, gluconic acid, adipic acid, maleic anhydride, fumaricacid, malonic acid, stearic acid, oleic acid, methacrylic acid, itaconicacid, sebacic acid, succinic acid, citric acid, tartaric acid, abieticacid, napthenic acid, palmitic acid, hydroxy acid, glycolic acid, lacticacid, ricinoleic acid, maleic acid, protocatechoic acid, garlic acid,cinnamic acid, hydroxycinnamic acid, caffeic acid, or bile acid.

In one preferred embodiment, the vehicle system additive comprises anaromatic amino salt, such as an aryl polyelectrolyte salt. Desirably,the salt comprising the vehicle system is a polyelectrolyte which is thereaction product of (1) a monomer; and (2) a photoinitiator that is acarboxylic acid containing compound. One preferred vehicle systemcomprises 2-benzophenone-carboxydimethylammoniumethylmethacrylate.

Advantageously, the vehicle system additive is safe, meets governmentalstandards and complies with environmental regulations. The vehiclesystem solves the problem discussed previously by replacing freemonomers with a functional polyelectrolyte that provides a specialvehicle system additive. This polyelectrolyte is unique in that it isstabilized as an amino salt which enables the polyelectrolyte to bewater soluble and also allows it to be compatible with a wide variety ofpolymer systems.

It has been discovered that this additive is very stable in waterborneemulsions and waterborne solution resins which contain less than onepercent isopropanol. It has also been discovered that thispolyelectrolyte can be activated by heat alone from a convection oven aswell as by UV radiation. A benefit of this technology is that it iseffective in concentrations as low as one percent, whereas in the priortechnology the polyelectrolyte often comprised 15 to 25% of theformulation.

The additive is manufactured by reacting the amino group in the monomerwith a carboxylic acid or anhydride-containing compound. The resultingproduct is believed to be a quaternary ammonium compound prepared byreaction of a carboxylic acid or anhydride-containing compound and anamino-functional methacrylate or acrylate monomer, with the generalformula:R

COO⁻)_(n)(⁺N—H—R′,R″,R′″⁻)_(n)wherein R is a “parent molecule,” COO⁻ is the reaction product formedfrom a carboxyl or anhydride group of the parent molecule, n is between1 and 10, and is preferably 1 to 4. The COO⁻ group or groups are derivedfrom a functional group or reactive site on the parent molecule. Anexample is an acid, such as benzophenone carboxylic acid, benzoic acid;4,4′bis(di-methylamino)-benzophenone;2,2′4,6′-tetrahydroxy-benzophenone, isoeuxanthonic acid;2,2′,5,6′-tetrahydroxybenzophenone; euxanthonic acid; benzenecarboxylicacid; 1,4-benzenedicarboxaldehyde; terephthalaldehyde;1,2-benzenedicarboxylic acid; 1,3-benzenedicarboxylic acid; isophthalicacid; 1,4-benzenedicarboxylic acid; terephthalic acid;2-aminobenzeneboronic acid; 2-amino-1,3-benzenedicarboxylic acid;1,3-benzenedicarboxylic acid; 4-bromo-1,3-benzenedicarboxylic acid;2-chloro-1,3-benzenedicarboxylic acid; 4,6-dichloro-1,3benzenedicarboxylic acid; 2,5-dichloro-1,3-benzenedicarboxylic acid;4,5-dimethoxy-1,3 benzenedicarboxylic acid;2-nitro-1,3-benzenedicarboxylic acid; tetrabromo-1,3-benzenedicarboxylicacid; benzenepentacarboxylic acid; 4,4′-carbonylbis (1,2-benzenedicarboxylic acid); 3,3′,4,4′-tetracarboxybenzophenone;3,3′4,4′-benzophenonetetracarboxylic acid (BTA); 4,4′-carbonyldiphthalicacid; benzophenonetetracarboxylic dianhydride; orthobenzoylbenzoic acid;or methanone benzoic acid; and is benzophenone in a preferred embodimentof the product. Benzophenone is also referred to as diphenylketone andhas a formula of (C₆H₅)₂CO.

Benzophenone is partially soluble in alcohol and ether. Benzophenone canbe used as an ultraviolet absorber for polymerization or as aninhibitor. In a mono-functional photoinitiator such as benzophenone, nin the above formula is one; in a tetra-functional photoinitiator, suchas BTA, n may be from one to four, depending on the stoichiometry of themixture and the degree of completion desired. Mono-anhydrides may havetwo functional attachment sites. For instance, when using the additivewill be more basic if more of such alkylamino acrylates or methacrylatesare added, and will more acidic if fewer are added.

b. Dialkylaminoalkyl Acrylate or Methacrylate Monomer

N⁺—H—R′,R″,R′″ is a quaternary ammonium component or salt formed from asubstituent of a dialkylaminoalkyl acrylate or methacrylate monomer, acompound that contains an amino functional group. In what is believed tobe an acid-base reaction with the carboxylic acid or anhydride compoundor photoinitiator, the acid furnishes the fourth group for thequaternary ammonium compound, a hydrogen ion or proton. The N is anitrogen atom from the dialkylaminoalkyl acrylate or methacrylatemonomer, the R′ group is an alkyl acrylate or methacrylate, and the R″and R′″ can be hydrogen, a dialkylaminoalkyl acrylate or methacrylate,or a saturated or unsaturated carbon group such as an alkyl, aryl,arylalkyl, alkane, alkene, alkadiene, napthene, or cycloolefin. TheN⁺—H—R′,R″,R′″ component can be derived, for example, fromN,N-dialkylaminoalkyl acrylate or N,N-dialkylamino-alkyl methacrylate,such as N,N-dimethylaminoethyl acrylate, N,N-dimethylaminoethylmethacrylate (MAME) or (DMAEMA); N,N-diethylaminoethyl acrylate;N,N-diethylaminoethyl methacrylate; N,N-diethylaminopropyl acrylate;N,N-diethylaminopropyl methacrylate; dimethylethylaminobutyl acrylate;or dimethylaminobutyl methacrylate.

Polyelectrolytes are high polymer substances either natural (protein gumarabic) or synthetic (polyethyleneimine, polyacrylic acid salts)containing ionic constituents. They may be cationic or anionic. Watersolutions of both types are electrically conductive. In apolyelectrolyte, ions of one sign are attached to a larger molecule orpolymer chain while those of the opposite sign are free to diffuse intothe solution. Polyelectrolytes are organic flocculants. A flocculent isa substance that induces flocculation. R″ and R′″ can be hydrogen, oneor more of the polyelectrolyte listed above, or saturated or unsaturatedcarbon groups, such as alkyl, aryl, arylalkyl, alkanes, alkanes,alkenes, alkadienes, napthenes, and cycloolefins. In the precedingformula, n is a number from 1 to 10, and is preferably 1 to 4. Theacidity or basicity (pH) of the additive may be tailored by tailoringthe stoichiometry of the acid/anhydride compound and the monomer used.

When mixing the components of the additive, it is important to keep thetemperature low, preferably well below room temperature. In this manner,only the amine portion of the monomer will react with the acid oranhydride, leaving the acrylate or methacrylate function available forlater reactions, such as flocculation. In addition to dialkylaminoalkylacrylate or methacrylate monomer, other monomers may also be used, suchas alkyl alkanolamine monomers. Examples are N,N-diethylethanolamine,N,N-dimethylethanolamine, N-methyl-N-ethylethanolamine, andN-methyl-diethanolamine

The additive is very stable in waterborne emulsions and waterbornesolution resins which contain less than 1% isopropyl alcohol, and verylow solvent contents in general. The technology preferably requires thatthe pH of waterborne systems be between 7 and 10 with the most preferredpH to be about 8 to 9.5. A benefit of this technology is that it iseffective in concentrations as low as 1%, whereas in the priortechnology the polyelectrolyte often comprised 15 to 25% of theformulation.

One useful photoinitiator is aromatic polycarboxylic acid having theformula C₁₇H₁₀0₉ with a weight of 358.26 g/mol, particularly4,4′-carbonylbis (1,2-benzene dicarboxylic acid);3,3′,4,4′-tetracarboxybenzophenone; 4,4′-carbonyldipthalic acid;3,3′4,4′-benzophenone-tetracarboxylic acid, known as BTA, such as soldunder the product name Allco BTA by Allco Chemical Corporation ofGalena, Kans. BTA has a melting point of 215-230° C. BTA dehydrates toform dianhydride near the melting point. BTA has a boiling point of380-400° C. as a dianhydride. BTA has a bulk density of 0.51 kg/L (32lbs/ft³) (dry powder) and a specific gravity of 1.46 at 26° C./20° C.BTA has a pH of 2.4 at 2.3 g/L (20° C.) and has a solubility in water of0.3 g/100 g at 26° C.

One useful polyelectrolyte methacrylate monomer isdimethylaminoethylmethacrylate, known as MAME or DMAEMA, such as thatsold by Allied Colloids Inc. of Suffolk, Va., also sold by Degussa.DMAEMA has a boiling point of 190° C., a vapor density of 5.4, aspecific gravity of 0.93, a vapor pressure of <1 at 26° C., and aflashpoint of 67° C. DMAEMA is a clear liquid with mild amine-like odorand is soluble in water. When BTA is used as the photoinitiator withDMAEMA, the resulting additive has no free monomers or only traceamounts of free monomers, i.e. less than 50 ppm. BTA produces betterresults than benzophenone tetracarboxylic dianhydride (BTDA).

Acrylic Resins

The term “acrylic” designates products obtained by the polymerization ofesters of acrylic (H₂C:CHCOOH) or methacrylic acid (H₂C:C(CH₃)COOH).These acids, and their nitrites and esters, are all included in theacrylic group. In addition to their clarity and unusual opticalproperties, acrylics generally have a low specific gravity, low waterabsorption, high dielectric strength, and good shock resistance.

Acrylic resins are thermoplastic polymers or copolymers of acrylic acid,methacrylic acid, or esters of these acids. Methylmethacrylate is anacrylic resin monomer that can be copolymerized with other methacrylateesters and many other monomers. Aqueous dispersions ofpolymethylmethacrylate can be used in water based paints. Solutions ofpolymethylmethacrylate in organic solvents can be used in protectivecoatings and light colored automobile lacquers.

Polymethylmethacrylate and methyl methacrylate have been produced underthe brand names and trademarks of: (a) Plexiglas by Rohm & Haas Co. ofPhiladelphia, Pa., and (b) Lucite by E.I. du Pont de Nemours & Companyof Wilmington, Del. Other companies also manufacturepolymethylmethacrylate and methyl methacrylate.

Monomeric methylacrylate can be produced by the reaction of aqueousmethyl alcohol with ethylene cyanohydrin which can be obtained by thereaction of ethylene oxide and hydrogen cyanide. Ethylacrylate can beproduced continuously by the addition of excess ethyl alcohol toacetylene in the presence of hydrogen chloride and nickel carbonyl.Monomeric methylmethacrylate can also be prepared from acetonecyanohydrin or by the esterification of methacrylic acid with methanolin the presence of phosphorus pentoxide. The methacrylic acid can beobtained by the catalytic oxidation of methacrolein which in turn isproduced by the vapor phase catalytic oxidation of methyl alcohol.

Polyacrylic and polymethacrylic acid can be produced by addition typepolymerization of the monomeric acids or by saponification of thepolymeric esters. These acids and their sodium salts are water-solubleand are used as thickening agents in water-based paints and printinginks. The copolymer of ethylacrylate and 2-chloroethyl vinyl ether or2-chloroethylacrylate can be cured by heating to give these materialsexcellent resistance to hot oils and oxidative degradation.Poly-1,1-hydroperfluorobutyl acrylate, a commercially availableelastomer, has excellent resistance to hot solvents and thermal andoxidative degradation. Methylcyanoacrylate is an effective adhesivesince it polymerizes in the presence of moisture or alcohol.

Acrylic Resin Solution

The acrylic resin solution can comprise, by weight, 20-50% acrylicsolution resin, 0-75% water, and 0-20% of an amine-containing,acrylic-cutting diluent, and preferably includes 25-45% acrylic solutionresin, 45-65% water, and 1-10% amine-containing acrylic-cutting diluent.For best results, the acrylic resin solution comprises, by weight,30-40% acrylic resin, 50-60% water, and 2-8% amine-containing,acrylic-cutting diluent. The acrylic solution resin preferably have anacid number of at least 180. The amine containing, acrylic-cuttingdiluent can comprise monoethanolamine (MEA), dimethanolamine (DMEA),triethanolamine (TEA), morpholine, propylene glycol, polypropyleneglycol, and preferably comprises ammonia (NH3) for best results.

The acrylic solution resin is preferably a styrene acrylic copolymer,such as that sold by the Noveon, Inc., of Cleveland Ohio, under thetrade name CARBOSET GA-1931. CARBOSET GA-1931 is a solution of acryliccopolymer in ammonia water, is 100% soluble in water, and has a boilingpoint of 100° C., a freeze point of 0° C. at a specific gravity of1.1-1.2, a vapor pressure of 17 mm Hg, and a vapor density of 0.62.CARBOSET GA-1931 contains less than 1% ammonia, less than 0.7% acrylicacid, less than 0.1% styrene, and less than 1% isopropyl alcohol.CARBOSET GA-1931 has the following properties: total solids of 41% byweight and 34.5% by volume; a pH of 8.5-9.2; a viscosity of 5000 cps(Brookfield at 25° C.); 9 lbs per gallon, a volatile organic content(VOC)<1%; and an acid number on solids of 190. CARBOSET GA931 is easy tohandle, has high gloss, exhibits excellent pigment wetting, gloss andresolubility, enhances flow and leveling, and is an outstanding pigmentdispersant.

Other acrylic solution resins from Noveon, Inc. are also useful. Theseinclude the solutions sold under the trade names CARBOSET GA-1926,CARBOSET GA-1993, CARBOSET XPD-2091. CARBOSET GA-1926 is an acryliccopolymer in ammonia water. CARBOSET GA-1993 is a styrene/acryliccopolymer in water with neutralized ammonia, and contains no less than1% ammonia and less than 0.05% styrene. CARBOSET XPD-2091 comprises45-55% acrylic polymer, 45-55% water, <0.01% acrylic acid, <0.01%styrene, and <0.1% isopropanol. CARBOSET XPD-2091 is 100% soluble inwater. Acrylic copolymer resins can be useful, such as those also soldby Noveon, Inc., of Cleveland Ohio, under the trade names CARBOSETGA-1161 and CARBOSET GA-1162.

Other acrylic solution resins can be useful, such as those sold byJohnson Polymer Co. of Sturtevant, Wis., under the trade name JONCRYL 60and 134 (Product Code 16540-5). JONCRYL 134 (Product Code 16540-5)comprises by weight: 30-40% styrene acrylic polymers, 60-70% water, 1-2%ammonium hydroxide, 1-55 urea, 1-3% polyoxyethylene block copolymer, and<0.99% styrene.

Other acrylic resins may be useful, such as those sold by Rohm & Haas,of Philadelphia, Pa., under the trade name MORCRYL 134 comprising astyrene acrylic solution. MORCRYL 134 has a pH of 8.5, a vapor densityof 1, a vapor pressure of 33 at 200° C., a specific gravity of 1; and aboiling point of 82° C.

Latex Resins

Latex or waterborne resins may be used in formulating a vehicle inembodiments of the present invention. A latex is generally defined as awater solution or emulsion (waterborne) of a synthetic rubber or plasticobtained by polymerization, and may also include natural or urethanesolutions or emulsions. For instance, a number of emulsions, primarilyof microcrystalline waxes are available for commercially for ink andcoating formulations. These waxes tend to be hydrocarbon-based, such aspolyethylene, polypropylene, or generally alkane or paraffin-based, andcombinations of one or more of polyethylene, polypropylene, and paraffinwaxes. One example is the Jonwax line of microcrystalline waxesavailable from Johnson Polymer, Inc., Sturtevant, Wis. The wax particlesin these emulsions may range from 50 to 4000 nm, and the solids loadingsmay vary considerably, at least from about 25 to 50 percent solids.Jonwax 4 and Jonwax 26 are two examples of waterborne waxes or resinsthat may be used in embodiments of the present invention. Jonwax 26 hasa 26% solids loading of a polyethylene wax dispersion having an averageparticle size of 53 nm. Jonwax 4 has a 40% solids loading of apolyethylene was dispersion having an average particle size of 4000 nm.These waterborne resins are well-known to those in vehicle arts forproviding rub and scuff resistance in water-based ink formulations. Theymay also be used in vehicles for other coatings, such as scuff-resistantpaints.

Urethane Resin Solution

In some circumstances, it may be desirable to use waterborne resins madefrom other chemical systems. For example, we have tested severalwaterborne urethanes as part of the first component of a vehicle system,the first component generally including one of an acrylic resinsolution, a latex resin solution, a vegetable oil, or a urethane. In oneembodiment, urethane resins in the form of aqueous dispersions areuseful. For instance, urethane dispersions containing from 30 to 51percent solids are available from a number of vendors. We havesuccessfully used at least Joncryl U4100 and U4188 (containingrespectively, 33 and 38 percent solids), from Johnson Polymer, Inc.,Sturtevant, Wis., in formulating paint vehicles. A number of othergrades are also available from this and other vendors. The urethanes areespecially helpful in formulating inks that allow dispersion of pigmentsin lower loading. If urethanes are used, it is preferable that they havevery minimal amounts of m-pyrrol and methylpyrrolidine.

Vegetable Oils

We have also discovered that vegetable oils may be used to preparevehicles for inks, paints, and coating in embodiments of the presentinvention. For example, linseed oils and oils made from soy may be used.A variety of pale and dark linseed oils are available from a number ofvendors. We have found that linseed oils from the Lawter International,Inc., of Pleasant Prairie, Wis., are suitable. Grades SR0000 to SR3, inDark and Pale grades, are highly useful, the dark grades having aGardner-Holdt color of 15 and the pale oils having a Gardner-Holdt colorof 10. All grades have an acid value of about 15 and a density of about7.9 lb/gallon. In the dark grades, viscosity varies from 70 to 5300 cp,while in the pale grades, viscosity ranges from 110 to 6900 poises, allreadings taken at 25° C. (77° F.). This range allows the user to tailorthe viscosity of the vehicle as desired. As is well known to users,offset lithographic and letterpress inks tend to be much more viscous orpasty than inks suitable for flexographic or gravure use. Thus, linseedoils in particular may be used to help adjust the viscosity of thevehicle to the desired range. Clearly, the linseed oils are very usefulin the higher viscosity ranges, as well as providing grades for the verylow viscosity ranges. The fact that soybean oils are sourced from arenewable source and are available world-wide is helpful in consideringtheir logistics for manufacture and sales everywhere.

Vegetable oils are typically fatty acids with a broad mixture ofcarbon-chain lengths and degrees of unsaturation, usually with one, twoor three carboxylic acid groups. Soybean oil, for instance typically hasabout 10-19% saturated fat (mostly C₁₆ and C₁₈) with a single carboxylicacid function, about 22-34 percent unsaturated C₁₈ with a singlecarboxylic acid functionality, and 50-60 percent unsaturated C₁₈ withtwo carboxylic acid groups and 2-10 percent unsaturated C₁₈ with threecarboxylic acid groups. Other vegetable oils have a constituency that issimilarly varied in terms of both unsaturation, molecular weight, andacid functionality. Accordingly, care should be paid to thestoichiometry of the particular batch that is used when preparing theadditive for use in embodiments of the present invention. Othervegetable oils that may be used include, without limitation, corn oil,cottonseed oil, olive oil, palm oil, palm kernel oil, peanut oil,linseed oil, tall oil, and tung oil.

Soybean oils may also be used, preferably refined soybean oils withimpurities and undesirable portions removed. Soybean oils are availablefrom a variety of refiners, including Cargill, Inc., Minneapolis. Minn.Preferred is the technical grade soybean oil. In order for easyprocessing, the oils are preferably degummed, refined, bleached anddeodorized. Other oils may also be used, such as tung oil, tall oil, andother vegetable oils well-known to those in art of preparation ofvehicles for inks, coatings, and paints.

Fumaric Resin Solution

The fumaric resin solution can comprise, by weight, 20-0% fumaric resin,also referred to as a fumaric solution resin, 0-75% water, and 0-30% ofan amine containing, fumaric-cutting diluting agent (diluent), andpreferably comprises 25-45% fumaric resin, 45-65% water, and 5-15% of anamine-containing, fumaric-cutting diluting agent. For best results, thefumaric resin solution comprises 30-40% fumaric resin, 50-60% water, and8-12% amine-containing, fumaric-cutting diluting agents. Fumaric resinis derived from pine tar. The preferred fumaric resin has an acid valueof 120-300 and most preferably has an acid value of at least 60.

The amine-containing, fumaric-cutting diluting agent can includedimethanolamine (DMEA), triethanolamine (TEA), ammonia, morpholine,propylene glycol, polypropylene glycol, and preferably comprisesmonoethanolamine (MEA) for best results. The amine ratio of the diluentsof monoethanolamine (MEA) in the fumaric solution resin to ammonia (NH3)in the acrylic solution resin can range from 1:1 to 10:1, preferablyfrom 3:1 to 6:1 for best results.

One preferred type of fumaric resin is sold by Akzo Coatings, Inc ofBaxley, Ga. under the trade name of FILTREZ 5014. FILTREZ 5014 is afumaric modified glycerol ester of rosin, and has a softening point of135-140° C. (R & B), an acid value of 160-180, a product density of 9.9lbs/gal., a VOC content of <1%, and a flash point of 425° F. (218° C.).Other fumaric resins may also be useful, such as grades FP 130, FP 171and FP 300, also available from Akzo Nobel.

Other fumaric resins can be useful, such as sold by AKZO Coatings, Incof Baxley, Ga. under the trade names of FILTREZ 643. FILTREZ 643 is asolution of resin modified polymers and hydrocarbon resin, and has a VOCcontent <1%. Other fumaric resins from other producers may also beuseful.

Acrylic Resin Emulsion

The acrylic resin emulsion can comprise, by weight, 50-100% acrylicemulsion resin and 0-30% water, and preferably comprises 60-90% acrylicemulsion resin and 5-25% water. For best results, the acrylic resinemulsion is 75%-85% acrylic emulsion resin and 10-20% water. The acrylicresin emulsion preferably comprises a dispersion of styrene acryliccopolymer emulsion in water, such as sold by Noveon, Inc, of Cleveland,Ohio, under the trade names CARBOSET GA-1086 and CARBOSET GA-1087.CARBOSET GA-1086 and GA-1087 contain less than 0.5% acrylic acid, lessthan 0.25% isopropyl alcohol, and less than 0.05% styrene, and have thefollowing properties: 48-49% total solids by weight, a pH of 8.6; aglass transition temperature of 40° C. and 105° C., respectively; aviscosity of 650-800 cps at 25° C. (Brookfield); and an acid number onsolid of 50. CARBOSET GA-1086 and GA-1087 are translucent, high glossand fast drying. CARBOSET GA-1086 exhibits excellent adhesion to varioussubstrates including flexible films and non-porous material and arewater resistant. CARBOSET GA-1087 has excellent alcohol compatibilityand is useful for inks and varnishes for paper and paperboard.

Other acrylic emulsion resins can be useful, such as others sold byNoveon, Inc. under the trade names CARBOSET GA-1166, CARBOSET GA-1161,and CARBOSET GA-1162. CARBOSET GA-1166 is a styrene acrylic copolymerdispersion in ammonia water, is soluble in alkaline water, and has thefollowing properties: a pH of 8.2 9.2, a boiling point of 100° C. avapor pressure of 17, a freeze point of 0° C., a vapor density of 0.62,and a specific gravity of 1.05 to 1.1. CARBOSET GA-1161 and CARBOSETGA-1162 can also be formulated into acrylic to copolymer emulsionresins. Other acrylic emulsion resins can be useful, such as those soldby Johnson Polymer Co. of Sturtevant, Wis., under the trade namesJONCRYL 77 and 89. JONCRYL 89 (Product Code 16360-4-6). JONCRYL 89(Product Code 16360-4-6) comprises by weight: 40-50% styrene acrylicpolymers, 2-3% ammonium hydroxide, <2% polypropylene glycol, and <0.2%styrene. Other acrylic emulsion resins may also be useful.

Defoamers

A defoamer is useful to reduce the foam in water based systems. Adefoamer is preferably added to the vehicle system on or before thevehicle is put on a printing press. One preferred defoamer comprises afluorochemical anionic surfactant, such as sold by 3M IndustrialChemical Products Division of the 3M Company of St. Paul, Minn. underthe trade name FC-129. This product is believed to be no longeravailable.

Other defoamers can be useful such as those sold by Tego Chemie ServiceUSA, a division of Goldschmidt Chemical Corp., of Hopewell, Va., underthe trade names TEGO Foamex 3062, TEGO Foamex 800, and TEGO Foamex 810.TEGO Foamex 3062 is a hydrophobic polysiloxane polyether copolymer. TEGOFoamex 3062 has a density of 1 g/cc at 200° C., a flash point of 100°C., and a weight of 8.3 lbs per gallon. TEGO Foamex 800 is an emulsionof a hydrophobic polysiloxane polyether copolymer. TEGO Foamex 800 isuseful for water-based paints, and has a density of 1 g/cc at 25° C., aviscosity of 600 cps, and a freezing point of 0° C.

Other defoamers useful for suppressing and minimizing foam aresilicon-based defoamers comprising polydimethylsiloxane that contains10% active silicone, such as produced under the brand name SAG 10antifoam by Univar Corp., of Seattle, Wash., USA. Other defoamers canalso be useful, such as the following antifoam emulsions and compoundsproduced by Univar: SAG 30 (30% active silicone), SAG 5 693(polyalkylene glycol/silicone), SAG 413 0, SAG 4220, SAG 544 1, SAG 710and SAG 730.

Other defoamers can be useful such as those sold by Air Products andChemicals, Inc of Allentown, Pa., under the brand names SURFYNOL DF-695and SURFYNOL DF-75. SURFYNOL DF-75 is useful for water-basedformulations in systems based upon acrylic resins, such as for aqueousinks, overprint varnishes, coatings, and adhesives. SURFYNOL DF-75 has aspecific gravity of 0.99, a pH of 8, a boiling point of 121° C., and aflash point of >204° C. SURFYNOL DF-695 is a silicone-based emulsiondefoamer and is useful in aqueous ink systems. SURFYNOL DF-695 has aspecific gravity of 1.01 to 1.04, a pH of 7.3, a viscosity of 9000 cpsat 25° C., and a boiling point of 100° C.

Inhibitors

An inhibitor can be used for vehicle transfer, storing and shipping toprevent spontaneous, rapid and undesired polymerization, as well as toprevent corrosion. An inhibitor can be added to the vehicle system toprevent liquid ink from sticking in the cells of Gravure cylinders inthe printing press. The inhibitor also serves as a lubricant. Theinhibitor further assists in the prevention of rust or oxidation ofmetal parts, in the printing press or other applicator.

One preferred inhibitor comprises acid phosphate/diethylamine salts,such as sold by Rhodia, Cranbury, N.J., under the trade name VIRCO PET40. VIRCO PET 40 comprises by weight: 30% phosphoric acid,mono-(2-hexyloxyethyl) ester, bis(diethylamine) salts; 60% phosphoricacid, bis (2-hexyloxyethyl) ester, diethylamine salts; and 10%diethylamine. Other inhibitors from Rhodia include VIRGO PET 30. VIRGOPet 30 is a mixture of a hydrogen phosphate compound, 2-butoxy ethanol,and other ingredients. These inhibitors may be thought of as coalescingagents, in the sense that they act to delay coalescence of the solution.This may be useful for prolonging the pot life or drying time ofarchitectural coatings or other products where desired. For instance, auser may wish to touch up a paint or a coating before it cures so thatthe finished product has a smooth, uniform appearance.

Surfactants

A surfactant can be added to the vehicle system to decrease surfacetension of the vehicle, increase transfer speed of the vehicle from theapplicator (e.g. printing press) to the substrate, enhance dispersion ofthe liquid and color dispersants (pigments), and improve spreading(trapping).

Anionic fluorochemical surfactants or fluorocompound wetting agents canalso help provide excellent adhesion of the product (vehicle system) tothe substrate. Some useful fluorosurfactants or fluorocompound wettingagents are those sold by 3M Company of St. Paul, Minn., under theFLUORAD brand names FC-4430 and FC-4432. These are believed to bepolymeric, non-ionic surfactants. Fluorosurfactants can be used alone orwith a hydrocarbon surfactant.

A caustic coupling surfactant, such as those sold by BASF Corporation,Mount Olive, N.J., under the brand name Mazon 40, can also be useful insome circumstances. Mazon 40 is a nonionic surfactant which is solublein water as well as in liquid caustic and other highly alkalinesolutions. Mazon 40 has a specific gravity of 1.15 at 25° C., a boilingpoint of 100° C., and a flash point of >93.3° C.

Other nonionic surfactants that can be useful are ethoxylatedsurfactants comprising ethoxylated acetylenic diols or ethoxylatedtetramethyldecynediol, such as those sold under the brand names SURFYNOL465 and SURFYNOL 485 by Air Products and Chemicals, Inc. of Allentown,Pa. SURFYNOL 465 and SURFYNOL 485 provide defoaming nonionic surfactantsand have a pH of 6-8. SURFYNOL 465 and SURFYNOL 485 exhibit good wettingperformance in paints, coatings, inks, adhesives, and emulsionpolymerization. SURFYNOL 465 contains 65% ethylene oxides by weight andhas a specific gravity of 1.038, a viscosity of <200 cps at 20° C., anda pour point of 6.67° C. SURFYNOL 485 contains 85% ethylene oxides byweight and has a specific gravity of 1.08, a viscosity of <350 cps at20° C., and has a pour point of 29° C.

Other fluorosurfactants can be useful surfactants, such as those sold byE.I. DuPont de Nemours & Company of Wilmington, Del., USA under theZONYL brand names FSP, FSE, FSJ, FSN, FSN-100, FSO, and FSO-100.

ZONYL FSO is a fluorinated surfactant comprising 50% telomer B monoetherwith polyethylene glycol, 25% ethylene glycol, 25% water, has a boilingpoint of 100° C., a vapor density of 2.1, a specific gravity of 1.3 andis 50% volatile. ZONYL FSP is a fluorinated surfactant including 20%isopropyl alcohol, 40-45% water and the balance telomer B phosphateammonium salt, with a specific gravity of 1.15, a pH of 6-8, and is 65%volatile. ZONYL FSN is a fluorinated surfactant with about 40%fluorosurfactant, 30% isopropyl alcohol, 30% water, a flash point of 22°C. (72° F.) (Pensky Martens closed cup method), a specific gravity of1.06, a pH of 7.5-8.5, and is 60% volatile.

Nonionic surfactants are surface active compounds which do not ionize ina water solution. Oftentimes, these surfactants possess hydrophiliccharacteristics by virtue of the presence therein of an oxygenated chain(e.g., a polyoxyethylene chain), the lyophilic portion of the moleculebeing derived from fatty acids, phenols, alcohols, amides or amines.Exemplary compounds are the poly(ethylene oxide) condensates of alkylphenols, e.g. the condensation product formed from one mole ofnonylphenol and ten moles of ethylene oxide, and the condensationproducts of aliphatic alcohols and ethylene oxide, e.g. the condensationproduct formed from 1 mole of tridecanol and 12 moles of ethylene oxide.

The nonionic surfactants can comprise phenol ethoxylates comprising acondensate product of ethylene oxide and an alkyl phenol or an aliphaticalcohol. The nonionic surfactants preferably comprise nonylphenolethoxylate such as T-DET-N, and/or octylphenol ethoxylate. The nonionicsurfactants are reaction products of ethylene oxide and nonylphenoland/or octylphenol. The ratio of the phenol to the ethylene oxide canrange from 2:20 to 4:16, and preferably is about 8:12.

Nonionic synthetic surfactants can comprise nonionic detergents.Nonionic synthetic surfactants can also be formed by condensing ethyleneoxide with a hydrophobic base formed by the condensation of propyleneoxide with propylene glycol. The hydrophobic portion of the moleculewhich, of course, exhibits water solubility has a molecular weight ofabout 1200 to 2500. The addition of polyoxyethylene radicals to thishydrophobic portion tends to increase the water solubility of themolecule as a whole and the liquid character of the product can beretained up to the point where polyoxyethylene content is about 50% ofthe total weight of the condensation product.

Other nonionic synthetic surfactants can include the polyethylene oxidecondensates of alkylphenols, e.g. the condensation products ofalkyphenols or dialkylphenols wherein the alkyl group contains fromabout 6 to 12 carbon atoms in either a straight chain or branched chainconfiguration, with ethylene oxide. The ethylene oxide can be present inamounts equal to 8 to 25 moles of ethylene oxide per mole ofalkylphenol. The alkyl substituent in such compounds 15 can be derivedfrom polymerized propylene, diisobutylene, n-octene, or n-nonene.

Nonionic surfactants can also be produced from the condensation ofethylene oxide with the reaction product of propylene oxide andethylenediamine, e.g. compounds containing from about 40% to about 80%polyoxyethylene by weight and having a molecular weight of from about5,000 to about 11,000 resulting from the reaction of ethylene oxidegroups with a hydrophobic base comprising the reaction product ofethylenediamine and excess propylene oxide; the base having a molecularweight on the order of 2,500 to 3,000.

Other nonionic surfatants include the condensation product of aliphaticalcohols having from 8 to 18 carbon atoms, in either straight chain orbranched chain configuration, with ethylene oxide, e.g. a coconut oilalcohol ethylene oxide condensation product having from 10 to 30 molesof ethylene oxide per mole of coconut alcohol, and the coconut alcoholfraction having from 10 to 14 carbon atoms.

Further nonionic surfactants include long chain tertiary amine oxidescorresponding to the following general formula: R₁R₃R₂N→O, wherein R₁,is an alkyl radical of from about 8 to 18 carbon atoms, and R₂ and R₃are each methyl or ethyl radicals. The arrow in the formula is aconventional representation of a semi polar bond. Examples of amineoxides suitable for use include dimethyldodecyl-amine oxide,dimethyloctylamine oxide, dimethyldecylamine oxide, anddimethylhexadecylamine oxide.

Other nonionic surfactants can include long chain tertiary phosphineoxides corresponding to the following general formula: RR′R″P→O, whereinR is an alkyl, alkenyl or monohydroxyalkyl radical ranging from 10 to 18carbon atoms in chain length, and R′ and R″ are each alkyl ormonohydroxyalkyl groups containing from 1 to 3 carbon atoms. The arrowin the formula is a conventional representation of a semi polar bond.Examples of suitable phosphine oxides are: dimethyldodecylphosphineoxide, dimethyltetradecylphosphine oxide, ethylmethyltetradecylphosphineoxide, cetyl dimethylphosphine oxide, dimethylstearylphosphine oxide,cetylethylpropylphosphine oxide, diethyldodecylphosphine oxide,diethyltetradecylphosphine oxide, dipropyl-dodecyl-phosphine oxide,bis(2-hydroxymethyl)dodecylphosphine oxide,bis(2-hydroxyethyl)-dodecylphosphine oxide,(2-hydroxypropyl)methyltetradecylphosphine oxide,dimethyldodecylphosphine oxide, and dimethyl-2-hydroxydodecylphosphineoxide.

It may be useful to use other surfactants, such as an anionicsurfactant, a cationic surfactant, an ampholytic surfactant or azwitterionic surfactant. The anionic surfactants comprise surface activecompounds. The anionic surfactants can contain hydrophilic and lyophilicgroups in their molecular structure which ionize in an aqueous medium togive anions containing the lyophilic group. Typical of these compoundsare the alkali metal salts of organic sulfonates or sulfates, such asthe alkali metal alkyl aryl sulfonates and the alkali metal salts ofsulfates of straight chain primary alcohols. Sodium dodecylbenzenesulfonate and sodium lauryl sulfate are typical examples of theseanionic surface active compounds.

Anionic surfactants can comprise synthetic detergents. Anionicsurfactants can include sodium alkyl sulfates, especially those obtainedby sulfating the higher alcohols (C₈ to C₁₈ carbon atoms) produced byreducing the glycerides of tallow or coconut oil; sodiumalkylglycerylethersulfonates, especially those ethers of the higheralcohols derived from tallow and coconut oil; sodium coconut oil fattyacid monoglyceride sulfates and sulfonates; the reaction product offatty acids esterified with isethionic acid and neutralized with sodiumhydroxide, where, for example, the fatty acids are derived from coconutoil; sodium or potassium salts of fatty acid amide of a methyltauride inwhich the fatty acids are derived from coconut oil.

The cationic surfactants can include cationic detergents. The cationicsurfactants comprise compounds which ionize in an aqueous medium to givecations containing the lyophilic group. Typical of these compounds arethe quaternary ammonium salts which contain an alkyl group of about 12to 18 carbon atoms, such as lauryl benzyl dimethyl ammonium chloride.

Ampholytic surfactants are compounds having both anionic and cationicgroups in the same molecule. Exemplary of such compounds are derivativesof aliphatic amines which contain a long chain of about 8 to 18 carbonatoms and an anionic water solubilizing group, e.g., carboxysulfo, sulfoor sulfato. Examples of ampholytic detergents are:sodium-3-dodecylaminopropane sulfonate, sodium-N-methyl laurate, andrelated substances such as higher alkyl disubstituted amino acids,betaines, sulfated long chain olefinic amines, and sulfated imidazolinederivatives.

Zwitterionic surfactants can include synthetic detergents. Zwitterionicsurfactants are generally derivatives of aliphatic quaternary ammoniumcompounds in which the aliphatic radical can be a straight chain orbranched, and wherein one of the aliphatic substituents contains fromabout 8 to 18 carbon atoms and one contains an anionic watersolubilizing group, e.g., carboxy, sulfo, or sulfato. Examples ofcompounds falling within this definition are 3-(N,N-dimethyl-N-hexadecylamino)-propane-1-sulfonate and 3-(N,N-dimethyl-N-hexadecylamino)-2-hydroxypropane-1-sulfonate. In some circumstances, it may bedesirable to use other types of defoamers, surfactants, and inhibitors.

Procedure

One procedure for producing a batch of the preferred additive for use ininks or a vehicle system is as follows:

1. Measure an amount of carboxylic acid, preferably 4,4′-carbonylbis(1,2-benzene-dicarboxylic acid), in the quantity for the batch sizedesired and pour into a container, such as a stainless steel pail.

2. Measure a sufficient quantity of water and dimethylaminoethylmethacrylate (MAME) for the selected batch size.

3. Place the stainless steel pail containing the BTA into a mixing tubon a drill press (mixer) and clamp the pail in place.

4. Fill the area around the pail in the mixing tub with ice andsufficient water to fill the mixing tub.

5. Install a mixing blade in the drill press.

6. Pour the water into the stainless steel pail containing the BTA.

7. Start mixing water and the BTA in the container by placing the mixingblades in the pail and rotating the mixing blades of the drill press ata medium speed. Reduce the temperature in the pail to 4° C. Weargoggles, mask, gloves, and coveralls. A white milky slurry will result.All the BTA may not be dissolved at this step, but it should be wellmixed.

8. Cover the pail and do the next step in a darkroom. Light will destroythe product from this point on.

9. Slowly add MAME into the pail as the BTA and water continues to mix.This step generates great amounts of heat. The mixture should not beallowed to go above 10° C. or it can be destroyed.

10. Once MAME is added, keep the product (mixture) below 10° C. for atleast two hours or less. Then remove the pail and allow the solutioncomprising the vehicle system additive to warm slowly to roomtemperature so it completes stabilization.

11. Package the vehicle system additive in an opaque container, such asa brown bottle. The vehicle system additive can be stored in a dark areaand will be stable for many years without degradation. Do not store itin the sunlight, excessive heat or under ultraviolet emitting light orthe additive may prematurely cure.

EXAMPLE 1

The above procedure was followed to prepare a batch of the additive.Specifically, 2.5 lbs. of water was added to 1 lb of4,4′-carbonylbis-(1,2-benzene-dicarboxylic acid), and agitated to form aslurry. Thereafter, 1.75 lbs dimethylaminoethyl methacrylate (MAME) wastrickled into the slurry in a darkroom. An exothermic reaction occurred.Trickling of MAME continued and the slurry reached a quasi-equilibriumstate and became milky. As the slurry became clearer, MAME was addedmore quickly. The resultant product (vehicle system additive) had nofree monomers and a pH of about 4.5. This additive should be bufferedbefore use by adding a small amount of isopropyl alcohol, usually a fewdrops, sufficient to bring the pH to about 8.5. Monoethanolamine may beused instead.

EXAMPLE 2

A stock solution of the additive was made by adding 20 grams oforthobenzoylbenzoic acid to 150 grams of water. The mixture was stirredand chilled to 40° C. To this mixture 13.85 grams ofdimethylaminoethyl-methacrylate (MAME) was added dropwise over a periodof 90 minutes. During the addition of the MAME, the temperature was keptbelow 12° C. The MAME reacted with the orthobenzoylbenzoic acid to formthe polyelectrolyte 2-benzophenone(carboxydimethylammonium-(ethylmethacrylate)) having the followingstructure:

The additive water solution was then allowed to reach room temperature.This solution was stored in brown glass bottles for use at a later date.

EXAMPLE 3

A vehicle system was formulated by combining the oligomer additive stocksolution of Example 2 with a fumaric resin (FILTREZ 5014) having an acidnumber over 170, an acrylic solution resin (CARBOSET GA-1931) and inkpigment dispersants. The ratio of fumaric resin to acrylic solutionresin is preferably about 2:1 to about 4:1; and is more preferably about3:1. A surfactant (e.g. SURFYNOL 465) was added to the vehicle system toreduce the surface tension from 72 dynes to 20 dynes. An inhibitor(VIRCO PET 40) and defoamer (FC-129) were also added to the vehiclesystem. The vehicle system comprised, by weight, 0.170 defoamer, 0.1%surfactants, and 0.2% inhibitors. The particle size of the blackpigments of the pigment dispersants were 5-8 microns. The resultantvehicle system had essentially no free monomers or VOCs. The vehiclesystem was applied as an ink to a Gravure printing press operating at2000 fpm at a depth less than 47 microns on the cylinders. The vehiclesystem transferred superbly onto paper at high speeds and did notundesirably stick, adhere or clog up the cylinders of the printingpress. The printing press printed four color high quality pages ofoutstanding quality. The finished product had a gloss rating of about85-90 degrees.

EXAMPLE 4

Coatings made with embodiments may be cured photochemically. The vehiclesystem of Example 3 was produced except that an acrylic emulsion resin(CARBOSET GA-1086) was used instead of fumaric resin and no additive wasused. The vehicle system was applied as a coating to polypropylene andheated under ultraviolet (UV) bulbs. The vehicle system flocculated, andhad essentially no VOCs or free monomers. The coating was cured, becamehard, indicating cross-linking, and produced a superb product.Reasonable line speeds were achieved using 4 300-W UV lamps. The vehiclesystem was then prepared using the additive of Example 2. Theformulation with the additive achieved the same line speed with a single600-W UV curing lamp.

EXAMPLE 5

In one experiment, a coating formulation according to Example 3 wasproduced. The coating was applied to a wood veneer, heated in an oven at150° F. (65° C.) for 5 minutes, and put into a UV (ultraviolet) tunnel.The coating was cured, became hard, and produced an excellent product.

EXAMPLE 6

A vehicle system was formulated as described in Example 5, but withpaint pigment dispersants. The resultant vehicle system had essentiallyno free monomers or VOCs. The resultant vehicle system was applied by aspray gun as a paint on the metal body of an automobile and dried byultraviolet (UV) heat lamps. The paint comprising the vehicle system hadsuperb adhesion to the metal. The paint comprising the vehicle systemalso had an excellent attractive finish and formed a secondary film toprevent the color from beaching and fading.

EXAMPLE 7

An adhesive is formulated as described in Example 5, but with anadhesive polymer, i.e. Rohm and Haas Co. PS-68 polymer, useful formaking pressure sensitive adhesives. Such a resin may act as aformulation for an adhesive. In one example, about 190.0 g adhesive isagitated and about 10.0 g of the additive of Example 1 is added slowly,making sure to control any exotherm. The resultant adhesive hasessentially no free monomers or VOCs. The vehicle system may be appliedas a pressure sensitive adhesive. The adhesive has excellent stickingand adhesive qualities, and because of the quicker coalescing, enablesfaster running of line speeds. One estimate is a three-fold increase,from about 200 feet per minute (FPM) to about 600 fpm in laminatingpaper.

The additive and vehicle system of this invention has producedunexpected surprisingly good results with inks, paints, coatings, andadhesives on numerous types of substrates including paper, paperboard,cardboard, clay coated board, metallic foils, films such as polyesterand polyolefin films, wood, glass, and plastic.

EXAMPLE 8

A stock solution of the additive was made by adding 20.0 grams oforthobenzoylbenzoic acid to 150 grams of water. The mixture was stirredand chilled to 40° C. To this mixture 7.0 grams of dimethylethanolaminewas added dropwise over a period of 90 minutes. During the addition ofthe dimethylethanolamine, the temperature was kept below 12° C. Theresulting vehicle is very useful for flexographic, gravure, or offsetlithographic inks.

EXAMPLE 9

A stock solution of the additive was made by adding 2.5 lb water to thevessel as described above, and stirring in 1.55 lb dimethylethanolamine.0.80 lb formic acid was added slowly, to control the exotherm. Sincenone of these species is a photoinitiator, the procedure need not becarried out in the absence of light. The resulting pH was about 8.5. Noadditional buffering was needed before combining with an ink or coatingfor printing.

EXAMPLE 10

Another stock solution of the additive was made by adding 2.50 lb waterto the vessel as described above for Example 9, and stirring in 1.83 lbdimethylethanolamine. 1.22 lb formic acid was added slowly, to controlthe exotherm. The resulting pH was about 8.5. No additional buffering isneeded before combining with an ink or coating for printing.

The additive is useful for the preparation of inks, coatings, paints andadhesives, as in above Examples 3-7. The additive may also be added insitu to improve the performance (flocculation) of inks. In one trial,the stock solution additive of Example 10 was added to the ink system ofan offset lithograph press, Speedmaster model, made by Heidelberg Press,between the second and third rolls of the ink system. The amount wasabout 2% by weight of the mass of ink in the system. As is well know,inks for lithographic printing are far more viscous than inks used inhigh volume processes, such as flexographic and gravure printing. As aresult of the additive, throughput was improved by at least 10% becauseof improved flocculating and drying of the ink.

In general, we have found that our additive may be added directly to webheat set inks on the press, such as those inks made with hydrocarbonoils. We have also found that adding the additive directly to the inksystem in offset lithography printing is also possible, especially withinks from vegetable oils, such as linseed oil or soybean oil. When theadditive is about 50% solids, an amount of about 2 weight percentadditive is sufficient to noticeably improve printing performance. Moreor less additive may also be used. Of course, the additive may also bemixed with an appropriate ink before the ink is charged to the press.

Additional Examples

Additional examples are presented in this section to show the greatapplicability of the additive. A vehicle for a water-based gravure inkmay be formed by mixing about 60% FILTREZ 5014, about 25% CARBOSETGA-1931, and about 3.75% modifier and 11.25% water. The ink made withsuch a vehicle is very flowable and may be used at very high speeds ongravure presses.

A waterborne vehicle for flexographic inks may be made with a similarformulation, with about 60% CARBOSET GA-1086, about 25% GA-1931, andabout 3.75% additive and 11.25% water. This vehicle readily forms inksthat dry and cure quickly on flexographic printing equipment.

A vegetable based ink vehicle may be made by adding 5% additive ormodifier to linseed or soybean oils. Alternatively, about 2% by weightof the modifier may be added to finished vegetable oil inks directly onthe ink system of printing machinery. Presses on which trials have beensuccessful include the Heidelberg Speedmaster model (Heidelberg,Germany), and one or more models from Komori Corp., Tokyo, Japan.

Water based coatings made be formulated by using a slightly greateramount of the additive. In one formulation, a coating is formed bymixing in about 40% high T_(g) emulsion, about 30% low T_(g) emulsion,about 10% high T_(g) resin, and about 3% wax and 5% modifier, and 12%water.

Paints may also be formulated directly with the additive. A water-basedpaint may be formed by adding 5-10% of the additive directly to anacrylic emulsion, a resin solution, a resin emulsion, a latex resinsolution, or a latex resin emulsion. An oil-based paint may beformulated by adding about 5-10% additive to a preferably refined anddegummed vegetable oil, such as linseed or soybean oil. Paints made withthe additive wet out pigment more effectively and have far less tendencyto agglomerate. Thus, these coating may use lower loadings of pigmentand are therefore more economical. These coating are also easy to applyand fast drying, with superior adhesion and greater hiding power.Coatings made with photoinitiator embodiments of the additive andapplied to aluminum siding had virtually no chalking or fading after upto five years of outdoor exposure. Adhesion to difficult substrates,such as polymeric substrates, is greatly improved in coatings made withthe additive.

Coatings

Two examples of coatings are presented, the coatings formulated with anadditive made according to Example 1, above. In these examples, theadditive was about 50% solids. In the formulations below, about 10% byweight additive was added to about 90% resin, by weight. Thus, in thefirst example, for an industrial maintenance glossy coating, 126.58 lbsof “Omnitech OT-204 Lot OH184” include 12.66 lbs of additive (50%solids) and 113.92 lbs Rohm & Hass Maincote HG-54D acrylic latex resin.In the second example, for a high quality interior flat, 59.67 lbs of“Omnitech OT-203 Lot OH-183” includes 5.97 lbs of additive (50% solids)and 53.70 lbs Rohm and Haas Rovace 9100 resin. The first coating ispresented in Table I and the second coating is presented in Table 2.

It is clear from the test results, especially the VOC content, that theadditive markedly improves the environmental acceptability of thecoatings. In addition, these low VOC coatings were excellent coatingsand applied easily.

TABLE I Industrial Glossy Maintenance Coating With additive, IngredientControl, wt. lbs. wt. lbs. Downal DPM 16.50 — Water 35.00 35.00 Tamol165 8.50 8.50 Aqueous ammonia (28%) 1.00 1.00 Triton CF-10 1.35 1.35TEGO 1488 1.35 1.35 DuPont R-902 175.00 175.00 Grind for 20 minutesMaincote HG-54D 595.00 464.77 Omnitech OT-204 Lot OH-184 — 126.58Aqueous ammonia (28%) 3.50 3.50 Butyl cellosolve 99.00 — TEGO 1488 2.352.35 Sodium nitrite 9.00 9.00 Water 21.72 21.72 TOTAL 969.27 850.12Lbs/gal 9.69 9.77 Weight percent solids 44.76 44.12 Volume percentsolids 34.64 34.65 Test results: VOC, grams/liter 285 15

TABLE II High Quality Interior Flat Coating With additive, IngredientControl, wt. lbs. wt. lbs. Water 300.00 300.00 Natrasol H4BR 2.00 2.00Trysan 186-II 1.80 1.80 Tamol 731 6.00 6.00 TEGO 1488 2.00 2.00 KTPP¹1.00 1.00 Triton NP-9 (N-101) 2.00 2.00 Triton N-57 2.00 2.00 PropyleneGlycol 45.00 — Huber 70C 75.00 75.00 DuPont R-902 200.00 200.00 CamelWhite 75.00 75.00 Grind for 20 minutes Rovace 9100 293.90 240.67Omnitech OT-203 Lot OH-183 — 59.67 Downal DPNB 13.00 — TEGO 1488 2.002.00 Water 64.44 112.83 Acrysol RM-825 19.00 19.00 Aqueous ammonia (28%)1.00 1.00 TOTAL 1105.14 1101.97 Lbs/gal 11.05 11.02 Weight percentsolids 47.76 47.68 Volume percent solids 30.76 30.76 Test results: VOC,grams/liter 196 17 ¹“Potassium tripolyphosphate” or pentapotassiumtriphosphate, K₅P₃O₁₀.

TABLE III Industrial Glossy Maintenance Coating w/ 0.6% w/ 1.0% w/ 1.3%Ingredients, pounds Control additive additive additive Downal DPM 15.357.68 3.84 — Water 35.00 35.00 35.00 35.00 Tamol 165 7.91 7.91 7.91 7.91Aq. ammonia (28%) 0.93 — — — Monoethanolamine — 0.93 0.93 0.93 TritonCF-10 1.26 1.26 1.26 1.26 TEGO 1488 1.86 1.86 1.86 1.86 DuPont R-902162.78 162.78 162.78 162.78 Grind 20 minutes Maincote HG-54D 553.44486.4 452.79 419.18 HG-54D/10% additive — 62.03 93.05 124.07 Ag. Ammonia(28%) 3.26 — — — Monoethanolamine — 3.26 3.26 3.26 TEGO 1488 2.79 2.792.79 2.79 Water 55.15 120.46 153.21 185.95 Butyl cellosolve “EB” 92.946.45 23.23 — Premix Water/sodium nitrite 4.00/8.00 4.00/8.00 4.00/8.004.00/8.00 Acrysol RM-12W 15.00 15.00 15.00 15.00 TOTAL, lbs. 959.63965.81 968.91 971.99 Lbs/gal 9.60 9.66 9.69 9.72 Weight percent solids42.35 42.18 42.10 42.02 Volume percent solids 32.56 32.57 32.57 32.57Test results: VOC, grams/liter 284 174 102 15

TABLE IV High Quality Interior Flat Coating Ingredients, pounds Controlw/ 0.55% additive w/ 3.0% additive Water 300.00 300.00 300.00 NatrosolH4BR 2.00 2.00 2.00 Troysan 186-II 1.80 1.80 1.80 Tamol 731 6.00 6.006.00 TEGO 1488 2.00 2.00 2.00 KTPP 1.00 1.00 1.00 Triton NP-9 (N-101)2.00 2.00 2.00 Triton N-57 2.00 2.00 2.00 Propylene glycol 45.00 — —Huber 70C 75.00 75.00 75.00 DuPont R-902 200.00 200.00 200.00 CamelWhite 75.00 75.00 75.00 Grind for 20 minutes Rovace 9100 293.90 240.67 —Additive, OH-203 — 59.67 332.2 Downal DPNB 13.00 — — TEGO 1488 2.00 2.002.00 Water 64.44 112.83 38.34 Acrysol RM-825 19.00 19.00 19.00 Aq.ammonia (28%) 1.00 1.00 1.00 TOTAL, lbs. 1105.14 1101.97 1092.66 Lbs/gal11.05 11.02 10.93 Weight percent solids 47.76 47.68 47.19 Volume percentsolids 30.76 30.76 30.76 Test results: VOC, grams/liter 196 17 17

TABLE V High Quality Exterior Satin Gloss Coating Ingredients, poundsControl w/ 0.85% additive w/ 3.9% additive Water 43.10 43.10 83.30Propylene glycol 40.00 — — Troysan 186-II 1.80 1.80 1.80 Tamol 731 10.0010.00 10.00 TEGO 1488 2.00 2.00 2.00 Triton CF-10 2.00 2.00 2.00Dimethylethanolamine 2.00 2.00 2.00 Mix for 10 minutes Huber 70C 60.0060.00 60.00 DuPont R-902 250.00 250.00 250.00 Grind for 20 minutesRhoplex AC-264 465.00 364.88 — 10% additive, OH-205 — 92.60 429.67 TEGO1488 6.00 6.00 6.00 Propylene glycol 35.00 — — Texanol² 14.00 — — Water157.06 251.29 238.35 Natrosol H4BR 3.98 3.98 3.98 TOTAL, lbs. 1091.941089.65 1089.10 Lbs/gal 10.92 10.90 10.89 Weight percent solids 55.2655.38 55.43 Volume percent solids 41.83 41.84 41.84 Test results: VOC,grams/liter 208 6 6 ²2,2,4-Trimethyl-1,3-pentanediol monoisobutyrate,C₁₂H₂₄O₃, CAS #25265-77-4.

Additional examples were also prepared to test the limits of theadditive, and are shown below in three additional tables. Table IIIshows how additional amounts of the additive progressively lowers VOC.In Table III, the additive included 70% acrylic emulsion, HG-54D, 10%water, 10% additive according to Example 1 above, and 2% S160(mildewcide, Ferro Corp., Walton Hills, Ohio).

Table IV, with a different acrylic emulsion, Rovace 9100 from Rohm &Haas, shows that as little as about 0.5-0.7% of the additive iseffective in lowering VOC with no corresponding loss of performance.

Table V, with a different acrylic emulsion, Rhoplex AC-264 from Rohm &Haas, provides another example with excellent performance. The additivein Table V was 90% Rhoplex AC264, 10% additive according to Example 1above. Tables I-V also show that coatings may be made from a vehicleusing only two components, the additive and the base resin, in thesecases an acrylic emulsion.

Advantages of the Additive

Among the many advantages of the vehicle system and additive of thisinvention are rapid high speed transfer between the press and thesubstrate to which the ink is applied. Other advantages include superbadhesion to the substrate, outstanding product performance, andexcellent protective coatings. With proper pigmentation, the coatingsmay prevent colors from fading, and are useful on many differentsubstrates. Because VOCs are virtually not used in the formulation,vehicles and inks, coatings, paints and adhesives will more readilycomply with environmental laws on airborne emissions, since there arevirtually no VOCs in the formulations. and thus will be beneficial tothe environment.

Vehicles and inks made with the additive have superior quality and freemonomers in the additive and the vehicle are decreased. Coatings andadhesives made with the additive have excellent strength. Inksflocculate quickly, dry quickly, and do not clog printing presses. Theadditive and vehicles made from the additive are easy to use. Inks andcoatings made with the additive or vehicles using the additive areattractive, economical reliable, safe, efficient and effective.

Although embodiments of the invention have been shown and described, itis to be understood that various modifications and substitutions, aswell as rearrangements of parts, components, and process steps, can bemade by those skilled in the art without departing from the novel spiritand scope of this invention. For instance, it is easier to control thereaction between the acid or anhydride with the acrylate, methacrylate,or amino compound of the additive, if a slurry or solution with the acidor anhydride is made first. This allows dissipation of the heat ofsolution of the acid, and allows for better mixing of high molecularweight carboxylic acids or anhydrides that are not very soluble, to forma slurry. Then, when the other compound is added, preferably dripwise orvery slowly, the exotherm is easier to control. However, the order ofaddition could be reversed with appropriate care to insure that the acidor anhydride, which may be in solid form, disperses well and does notcause an explosive exotherm. Both methods of forming the additive aremeant to be included as embodiments.

While it is typical to form a vehicle for inks or paints in a mixingvessel, and then to incorporate the vehicle into a formulation for anink, a paint, a coating, and so forth, it has been shown that theadditive may be prepared separately and added to the inking system of aprinting press. This method of addition to form an ink, paint, coating,and so forth, are embodiments, as is the ink, paint, coating, and soforth that are formed in this manner.

It will also be understood that inks, paints, coatings and adhesives mayinclude many other components not discussed herein, and well-known tothose skilled in the art. For example, vegetable oil compositions, suchas those using linseed oil, may require catalysts or activators tooxidize or cure. These may include one or more of cobalt acetate,manganese acetate, calcium stearate, or other activators, such as thoseusing rare-earth elements. Embodiments of the invention will includesuch well-known components otherwise necessary for the properfunctioning and performance of compositions made with the vehicle oradditive described above.

It is therefore intended that the foregoing detailed description beregarded as illustrative rather than limiting, and that it be understoodthat it is the following claims, including all equivalents, that areintended to define the spirit and scope of this invention.

1. A vehicle system, comprising by weight relative to the vehiclesystem: (a) about 4-45% of a first component, the first componentcomprising at least one material selected from the group consisting ofan acrylic resin solution, a latex dispersion, a urethane solution, amicrocrystalline wax solution, and a vegetable oil; (b) about 50-90% ofa second component, the second component comprising at least onematerial selected from the group consisting of a fumaric resin solutionand an acrylic resin emulsion; and (c) about 0.5-10% of an aqueoussolution of an additive comprising the reaction product of (i) a firstreagent comprising a carboxylic acid; and (ii) a second reagentcomprising at least one material selected from the group consisting of adialkylaminoalkyl acrylate monomer, and a dialkylaminoalkyl methacrylatemonomer.
 2. The vehicle system of claim 1, wherein the additive iscapable of being activated by heat to cause phase separation of thevehicle system.
 3. The vehicle system of claim 1, wherein the additiveis capable of being cured photochemically.
 4. The vehicle system ofclaim 1, wherein the first component comprises acrylic resin solution,the second component comprises a fumaric resin solution, and the weightratio of fumaric resin to acrylic resin is from about 2:1 to about 4:1.5. The vehicle system of claim 1, wherein the first component comprisesabout 2-50% by weight of acrylic resin, water up to about 75% by weight,and about 0-20% by weight of a diluting agent.
 6. The vehicle system ofclaim 1, wherein the second component comprises about 2-50% by weight offumaric resin, water up to about 75% by weight, and about 0-30% byweight of a diluting agent.
 7. The vehicle system of claim 1, whereinthe first component comprises a urethane dispersion of about 25 percentto about 50 percent by weight solids in an aqueous solution.
 8. Thevehicle system of claim 1, wherein the first component is selected fromthe group consisting of corn oil, cottonseed oil, olive oil, palm oil,palm kernel oil, peanut oil, linseed oil, soybean oil, tall oil, andtung oil.
 9. The vehicle system of claim 1, wherein the second componentcomprises about 50-100% by weight acrylic emulsion resin and water up toabout 30% by weight.
 10. A paint, ink, or coating comprising the vehiclesystem of claim
 1. 11. A paint, ink, or coating comprising the vehiclesystem of claim 1, further comprising at least one of i) a surfactant inan amount of about 0.05 to 0.5 weight percent; ii) a defoamer in anamount of about 0.05 to 0.5 weight percent; and iii) an inhibitor in anamount of about 0.05 to 2.0 weight percent.
 12. A vehicle system,comprising by weight relative to the vehicle system: (a) about 4-45% ofa first component comprising at least one material selected from thegroup consisting of an acrylic resin solution, a latex dispersion, aparaffin solution, a paraffin emulsion, a urethane resin solution and avegetable oil; (b) about 50-90% of a second component comprising atleast one material selected from the group consisting of a fumaric resinsolution and an acrylic resin emulsion; and (c) about 0.5-10% additivein aqueous solution comprising the reaction product of (i) a firstreagent comprising carboxylic acid and containing a benzene ring; and(ii) a second reagent comprising at least one material selected from thegroup consisting of an alkylaminoalkyl acrylate monomer and analkylaminoalkyl methacrylate monomer.
 13. An ink, coating, or adhesivemade with the vehicle according to claim
 12. 14. A vehicle system,comprising by weight relative to the vehicle system: (a) about 80-99% ofa first component comprising at least one material selected from thegroup consisting of an acrylic resin solution, a urethane resinsolution, a latex dispersion, a wax dispersion or emulsion, a fumaricresin solution, and a vegetable oil; and (b) about 1-20 additivecomprising in aqueous solution the reaction product of (i) a firstreagent comprising a carboxylic acid; and (ii) a second reagentcomprising at least one material selected from the group consisting of adialkylaminoalkyl acrylate monomer, and a dialkylaminoalkyl methacrylatemonomer.
 15. The vehicle system of claim 14, wherein the second reagentis selected from the group consisting of N,N-dimethylaminoethylacrylate, N,N-dimethylaminoethyl methacrylate; N,N-diethylaminoethylacrylate, N,N-diethylaminopropyl acrylate, N,N-dimethylaminoethylmethacrylate, N,N-diethylaminoethyl methacrylate, N,N-diethylaminopropylmethacrylate, N,N- diethylaminopropyl acrylate; N,N-diethylaminobutylmethacrylate; and N,N-diethylaminobutyl acrylate.
 16. The vehicle systemof claim 14, wherein the additive comprises the reaction product of3,3′,4,4′-benzophenonetetracarboxylic acid andN,N-dimethylaminoethyl-methacrylate.
 17. The vehicle system of claim 14,wherein the first component comprises about 50-100% by weight acrylicemulsion resin and water up to about 30% by weight.
 18. An ink, coating,or adhesive made with the vehicle according to claim
 14. 19. The paint,ink, or coating of claim 14, further comprising at least one of aninhibitor in an amount of about 0.05 to 2.0 weight percent, a surfactantin an amount of about 0.05 to 0.5 weight percent, and a defoamer in anamount of about 0.05 to 0.5 weight percent.
 20. An ink comprising thevehicle system of claim 1, wherein the first component is an acrylicresin solution; wherein the second component is a fumaric resinsolution; wherein the first reagent is a carboxylic acid; and whereinthe second reagent is a dialkylaminoalkyl methacrylate.